CA1263021A - Pressure sensitive copy material - Google Patents
Pressure sensitive copy materialInfo
- Publication number
- CA1263021A CA1263021A CA000526101A CA526101A CA1263021A CA 1263021 A CA1263021 A CA 1263021A CA 000526101 A CA000526101 A CA 000526101A CA 526101 A CA526101 A CA 526101A CA 1263021 A CA1263021 A CA 1263021A
- Authority
- CA
- Canada
- Prior art keywords
- solvent
- pressure sensitive
- phenyl
- coupler
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
Landscapes
- Color Printing (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a pressure sensitive copy material using an electron accepting developer and an electron donating coupler which develops a color by contacting with the developer, the pressure sensitive copy material being characterized by employing phenyl-sec-butyl-phenyl-methane as a solvent for the electron donating coupler.
The present invention provides a pressure sensitive copy material using an electron accepting developer and an electron donating coupler which develops a color by contacting with the developer, the pressure sensitive copy material being characterized by employing phenyl-sec-butyl-phenyl-methane as a solvent for the electron donating coupler.
Description
3~2,3~.
SPECIFICATION
Il 1' l~ THE INVENTION
Pressure Sensitive Copy Material BACKGROUND OF THE INVENTION
(1) Field of the Invention _ _ The present invention relates to a record material, more particularly to a pressure sensitive copy material.
~2~_ Description of the Prior Art Heretofore, record materials, i.e., pressure sensitive copy papers have been known which are each composed of a paper coated on the one side thereof with microcapsules containing a colorless electron donating agent (hereinafter referred to as the coupler~ in a liquid state therein and another paper coated on the one side thereof with an 15 electron accepting substance ~hereinafter referred to as the developer) such as a clay~or a polymeric material having an :
ability to develop a color by the reaction with the aforesaid coupler. When used,~both the papers are super-~;~ posed on each other so that the respective coated surfaces thereof may face each other, and a pressure is then applied -~ ~ onto the superposed papers, so that a copy record is `~ ~ given thereby.
:
This type of record material has the following copy record mechanism: The microcapsules on the paper are '' ~3~
ruptured by the pressure from a pen, a typewriter or the like in order to release a coupler solution therefrom,.and the latter is then brought into contact w.ith the developer with wh.ich the confronted paper has been coated, whereby a color is developed.
Further, another type of xecord material has been known in which the respective coating layers having such a color developing mechanism as described above are formed onto either sur~ace of one paper, the microcapsule layer and the developer layer being disposed as an inside layer and an outside layer, respectively. In the case of this record material, the microcapsules, when used, are broken by a pressure from a pen, a typewriter or the like to conse-quently release a coupler solution therefrom, and the latter , , ~ 15 then contacts with the developer of the outside layer, thereby developing a color~
: The coupler solution used in the aforesaid record material is a solution in which the electron donating coupler is dissolved in one or more hydrophobic solvents ~20 The hydrophobic solvent used herein is required to satisfy the following requirements.
: ~ That is, these requirements are to be nontoxic; to have no uncomfortable odor; to be colorless or to have an : extremely faint color; to be nonvolatile; to dissolve the coupler sufficiently; to be excellent in stability, after ..
. ,.
3~
having dissolved the coupler; to be able to change into minute dispersions, when microcapsuled; to permit encapsu-lating the minute dispersions; to ensure a storage stability of the microcapsules; to permit coating a sheet material with the microcapsules uniformly with a suitable thickness;
to allow a color developing reaction to occurs, when the coupler contacts with the developer, and to accelerate a color development velocity; when a paper is coated with a polymeric material which is the developer, to dissolve the polymeric material so as to enable a close contact with the coupler; to permit providing sharp color-developed images without blotting; and even after stored for a long period of time, to ensure the formation of the clear color-developed images.
Examples of the already known and industrially used : solvents for the coupler in this kind of pressure sensitive copy mat.erial include diarylalkanes such as phenyl-xylyI-ethane, phenyl-isopropylphenylethane, phenyl-xylyl-methane;
an alkylnaphthalene such as diisopropylnaphthalene; an alkylbiphenyl such as isopropylbiphenyl; and partially ~hydrogenated terphenyl. ~:
In addition, as the solvents for the coupler, various dlarylmethanes and diarylethanes have been suggested in U.S.
Patent No~ 3,836,383, 3apanese Patent Provisional Publica-tlon No~ 15,613/1973 and U.K. Patent No. 1,389,674.
~ ~;30;2~
However, these suggested solvents do not satisfy the above mentioned requirements for the solvent, in particular, the requirements of the color development properties and the inhibition of an odor simultaneously.
-~ 5 Generally speaking, the solvent having a high color development velocity is low in boiling point and is strong in odor. Inversely, the solvent having a less odor is high in boiling point and a viscosity, and is poor in color development properties.
SUMMARY OF_THE INVENT
The present invention intends to provide a pressure sensitive copy material which can solve the above mentioned problems of the conventional solvent for a coupler and which has an excellent color development performance and a less odor.
;The inventors of the present application have conducted researches on StrDCtUres of alkylene and alkyl groups of various diarylalkanes, thair~physical properties, and relations between these factors and performance in the case 20~ that they are used as the solvents for the coupler in the pressure sensitive copy material. As a result, it has been found that the color development performance is higher when ~the alkylene group is a methylene group than when it is an ethylidene group or an ethylene group, and that the higher the color development performance is, the smaller the number ~ 4 -.
~6~n~
of substituted alkyl groups on a benzene ring is and the lower the branching coefficient of the alkyl group is. In consequence, the present invention has now been completed on the basis of this knowledge.
Moreover, the present inventors have also found that among the C4 alkyl groups, a sec-butyl group is suitable.
That is, the present invention intends to provide a solvent used in the pressure sensitive copy material which is excellent in color development intensity and a color development velocity and which can be manufactured at a low cost.
The present invention is directed to a pressure sensitive copy material using an electron accepting developer and an electron donating coupler which develops a color by contacting with the developer, the pressure sensitive copy material being characterized by employing phenyl-sec-buty~lphenyl-methane~as~a solvent for the electron donating coupler which develops the color by contacting with the electron accepting~developer.
:~20 ~ DESCRIPTIaN OF THE PREFERRED EMBODIMENT
PhenyI-sec-butylphenyl-methane can be prepared by any known method. For example, there are a method of alkylating diphenylmethane by the use of normaI butene in the presence of an acid catalyst, a method of benzylating sec-butylben-zene likewise with the aid of an acid catalyst, a method of condénsing benzene and sec-butylbenzene with formalin, and the like. However, the present invention should not be limited to these methods.
The above mentioned phenyl-sec-butylphenyl-methane can be manufactured more lnexpensively than, for example, phenyl-n-butylphenyl-methane or the like.
Phenyl-sec-butylphenyl-methane has three position isomers of ortho-, meta- and para-compounds owing to substitution positions of the sec-butyl group, and all of these isomers can be used in the present invention.
Nevertheless, the solvent containing plenty of the meta-isomer, the para-isomer or a mixture thereof is desirable from the viewpoints of a color development performance and the like, and the total amount of the meta- and para-isomers in the solvent is preferably 50% by weight or more, more preferably 60% by weight or more. Such a suitable solvent can be easily prepared by altering reaction conditions in the above mentioned manufacturing methods.
The solvent of the present invention can be used, of course, alone and in 50 far as the properties of the solvent itself are not impaired, together with an auxiliary solvent such as a kerosine fraction, an isoparaffinic solvent~ a normal paraffinic solvent, a naphthenic solvent or an alkylbenzene.
In addition thereto, a solvent prepared by mixing the ~3~
phenyl-sec-butylphenyl-methane with another known solvent for a coupler can also be employed in the present invention.
As colorless or nearly colorless electron donating couplers which can develop a color by contacting with a developer, there are typically triarylmethane type com-pounds, diphenylmethane type compounds, xanthene type compounds, thiazine type compounds, and spiropyran type compounds.
The dye-precursors of triarylmethane type compounds are exemplified by 3,3-bis(p-dimethylaminophenyl)-6-dimethyl-aminophthalide (Crystal Violet Lactone), 3,3-bis(p-dimethyl-aminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methyIindole-3-yl)phthallde, 3-~p-dimethylaminophenyl)-3-;~ 15 (2-phenylindole-3-yllphthalide, 3~,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis(1 r 2-dimethylindole-3-yl)~-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl~-S-dimethylaminophthal1de, 3,3-bis(2-phenylindole-3-yl)-5-dlmethylaminophthalide, and 3-p-dimethylaminophenyl-3 (1-methylphrrole-2-yl)-6-dimethy~aminophthalide.
The dye-precursors of diphenylmethane type compounds are exemplified by 4j4-bis-dimethylaminobenzhydrine benzyl ether, N-halophenyl leuco Auramine, and N-2,4,5-trichloro-phenyl leuco Auramine.
The xanthene type dye-precursors are exempllfied by ~, ~
Rhodamine B-anilinolactam, Rhodamine B-(p-nitroanilino)-lactam, Rhodamine B-(p-chloroanilino)lactam, 3-dimethyl-amino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chloro-6-methylfluoran, 3-diethylamino-7-(acetylmethylamino)fluoran, 3-diethylamino-7-(dibenzylamino)-fluoran, 3-diethylamino-7-(methylbenzylamino)fluoran, 3-diethylamino-7-(chloroethylmethylamino)fluoran, 3-diethyl-amino-7-(diethylamino)fluoran, and 3-diethylamino-6-methyl-7-anilinofluoran.
The thiazine type dye-precursors are exemplified by benzoyl leuco methylene blue and p-nitorbenzoyl leuco methylene blue.
The spiro type dye-pxecursors are exemplified by 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphtho-pyran, 3-methylnaphtho-(3-methoxybenzo)spiropyran, and 3-propyl-spiro-dibenzodipyran.
The coupler can be dissolved into the solvent of the i invention in the manner ]ikewise the use of conventional solvents.
As electron accepting color developers, there are clay, polymers, and aromatic carboxylic acids or their metal salts.
The polymers ale exemplified by phenol-aldehyde polymer, phenol-acetylene polymer, maleic acid-rosin .
-polym`er, partially or completely hydrolyzed styrene-maleic anhydride copolymer, partially or completely hydrolyzed ethylene-maleic anhydride copolymer, carboxy polyethylene, and partially or completely hydrolyzed vinyl rnethyl ether-maleic anhydride copolymer.
The examples of aromatic carboxylic acids and their derivatives are exemplified by 3,5-di(~-methylbenzyl)-salicylic acid, 3-(~-methylbenzyl)-5-(~,~-dimethylbenzyl)-salicylic acid, 3-(4'~ dimethylbenzyl)phenyl-5-(~
dimethylbenzyl)salicylic acid, 3,5-di-tert-butyl salicylic acid, 3,5-di-tert-octyl salicylic acid, 3-cyclohexyl-5-(~
dimethylbenzyl~salicylic acid, 3-phenyl-5-(~,~-dimethyl-benzyl)salicylic acid, and 3,5-dit~,Q-dimethylbenzyl)-salicylic acid. Furthermore, their salts of polyvalent metals such as zinc, aluminum, barium, tin, iron, calcium and lead can also be used.
In addition, as the electron accepting developers, there are exemplified by bentonite, zinc oxide, tatanium : oxide, kaolin,~active china clay, acidic china clay, zeolite, talc and colloidal silica.
The above mentioned coupler, when used, is dissolved in a solvent of the present invention, but an amount of the dissoled coupler is generally within the range of 0.5 to 15%
by weight or so.
As the copy material of the present invention, a ~
_ g 63~
pressure sensitive copy material, for example, a pressure senstive copy paper is now picked up, and its generic manufac-turing method will be described: A solution in which the aforesaid coupler is dissolved in the solvent of the present invention is emulsified and dispersed in a mixed aqueous solution of gelatin and gum arabi, and gelatin coatings are then formed around emulsified oil drops by means of the coacervation method. In recent years, an interfacial polymerization, an in-situ polymerization and the like can often be employed for the formation of resin coatings. A first paper is then coated with the thus formed capsule emulsion of the fine oil drops. Afterward, a second paper is coated, on its surfacé which will confront the above coated surface of the first paper, with the aforesaid , 15~ developer, or alternatively the above mentioned first paper is further coated, on the already coupler-coated surface thereof, with the aforesaid developer ln the form of a layer, so that the desired pressure sensitive copy paper can be manu~actured.
Example By the use of a cation exchange resin (Amberlist-15;
Rhoom & Haas Co., Ltd.), diphenylmethane was allowed to react with normal butene in order to prepare phenyl-sec-butylphenyl-methane.
This product had a boiling point of 301 to 312C and a .
~3~2~
kinematic viscosity of 3.9 c.s. at 40C. The total content of meta- and para-isomers in the product was about 80% by weight. In this solvent, CVL which was a coupler was dissolved as much as an amount of 5% to obtain a coupler solution.
This solution was then changed into microcapsules in accordance with the complex coacervation method using gelatin. With the thus obtained microcapsule emulsion, a fine paper was coated to prepare an upper paper.
On the other hand, another paper was coated with a phenolic resin which was a developer, in order to prepare a lower paper.
The prepared upper and lower papers were superposed on each other so that the microcapsule coated surface of the upper paper might face the developer coated surface of the lower paper, and a high pressure press was then driven to develop a color all over the surface.
The lower paper was measured for its reflectance at room temperature by the use of a reflection type spectro-photometer 30 seconds, 60 seconds and 60 minutes after the press operation, in order to thereby obtain color develop-ment intensities.
~ The results are set forth in Table 1. Additionally, the judgment results of odors are listed together.
Each odor judgment result was represented by the total :. -~302~
point of 10 judges on the basis of the standard of "a strong bad odor" being -1 point, "a bad but allowable odor" being 0 point and "no bad odor" being 1 point.
Eor comparison, as diarylethanes having the same carbon S number as in the above Example regarding the present invention, there were used 1-phenyl-1-(isopropylphenyl)-ethane (solvent A), 1-phenyl-2-(isopropylphenyl)ethane (solvent B) and phenyl-tert-butylphenyl-methane (solvent C), and the results are set forth in columns of Comparative Examples 1 to 3 in Table 1. It is apparent ~rom the results therein that the Comparative Examples all had poorer color development properties than in the Example regarding the present invention.
Further, Comparative Examples 4 to 7 were concerned with bicyclic aromatic hydrocarbon solvents having a less carbon atom number than in the ~xample of the present case.
A solvent D was phenyl-xylylethane, a solvent E was phenyl(ethylphenyl)ethane, a solvent F was benzyl-ethyl-benzene and a solvent G was diisopropylnaphthalene.
The solvents E and F were excellent in the color development properties, but were poor in odor inhibition.
The solvent D had poorer color development properties than in the above Example. The solvent G was excellent in odor inhibition but poor in color development properties. In short, the solvents used in the present invention have more . .
~3(1~2~
excellent color development properties and odor inhibition, as compa.red with the conventionally used solvents i.n the Comparative Examples. Comparing with the solvents of Comparative Examples 1, 2, 3, 4 and 7, the excellent color development properties which the solvents of the present invention have are more remarkable at temperatures lower than room temperature.
Table 1 Color Devel.
Intensity (%) Color Devel.
After Aftex After Velocity Solvent 30 sec 60 sec 60 min Ratio(~) Odor _ _ .
Example Better Better Better Better 8 Comparative Example 1 A Good Good Better Good 6
SPECIFICATION
Il 1' l~ THE INVENTION
Pressure Sensitive Copy Material BACKGROUND OF THE INVENTION
(1) Field of the Invention _ _ The present invention relates to a record material, more particularly to a pressure sensitive copy material.
~2~_ Description of the Prior Art Heretofore, record materials, i.e., pressure sensitive copy papers have been known which are each composed of a paper coated on the one side thereof with microcapsules containing a colorless electron donating agent (hereinafter referred to as the coupler~ in a liquid state therein and another paper coated on the one side thereof with an 15 electron accepting substance ~hereinafter referred to as the developer) such as a clay~or a polymeric material having an :
ability to develop a color by the reaction with the aforesaid coupler. When used,~both the papers are super-~;~ posed on each other so that the respective coated surfaces thereof may face each other, and a pressure is then applied -~ ~ onto the superposed papers, so that a copy record is `~ ~ given thereby.
:
This type of record material has the following copy record mechanism: The microcapsules on the paper are '' ~3~
ruptured by the pressure from a pen, a typewriter or the like in order to release a coupler solution therefrom,.and the latter is then brought into contact w.ith the developer with wh.ich the confronted paper has been coated, whereby a color is developed.
Further, another type of xecord material has been known in which the respective coating layers having such a color developing mechanism as described above are formed onto either sur~ace of one paper, the microcapsule layer and the developer layer being disposed as an inside layer and an outside layer, respectively. In the case of this record material, the microcapsules, when used, are broken by a pressure from a pen, a typewriter or the like to conse-quently release a coupler solution therefrom, and the latter , , ~ 15 then contacts with the developer of the outside layer, thereby developing a color~
: The coupler solution used in the aforesaid record material is a solution in which the electron donating coupler is dissolved in one or more hydrophobic solvents ~20 The hydrophobic solvent used herein is required to satisfy the following requirements.
: ~ That is, these requirements are to be nontoxic; to have no uncomfortable odor; to be colorless or to have an : extremely faint color; to be nonvolatile; to dissolve the coupler sufficiently; to be excellent in stability, after ..
. ,.
3~
having dissolved the coupler; to be able to change into minute dispersions, when microcapsuled; to permit encapsu-lating the minute dispersions; to ensure a storage stability of the microcapsules; to permit coating a sheet material with the microcapsules uniformly with a suitable thickness;
to allow a color developing reaction to occurs, when the coupler contacts with the developer, and to accelerate a color development velocity; when a paper is coated with a polymeric material which is the developer, to dissolve the polymeric material so as to enable a close contact with the coupler; to permit providing sharp color-developed images without blotting; and even after stored for a long period of time, to ensure the formation of the clear color-developed images.
Examples of the already known and industrially used : solvents for the coupler in this kind of pressure sensitive copy mat.erial include diarylalkanes such as phenyl-xylyI-ethane, phenyl-isopropylphenylethane, phenyl-xylyl-methane;
an alkylnaphthalene such as diisopropylnaphthalene; an alkylbiphenyl such as isopropylbiphenyl; and partially ~hydrogenated terphenyl. ~:
In addition, as the solvents for the coupler, various dlarylmethanes and diarylethanes have been suggested in U.S.
Patent No~ 3,836,383, 3apanese Patent Provisional Publica-tlon No~ 15,613/1973 and U.K. Patent No. 1,389,674.
~ ~;30;2~
However, these suggested solvents do not satisfy the above mentioned requirements for the solvent, in particular, the requirements of the color development properties and the inhibition of an odor simultaneously.
-~ 5 Generally speaking, the solvent having a high color development velocity is low in boiling point and is strong in odor. Inversely, the solvent having a less odor is high in boiling point and a viscosity, and is poor in color development properties.
SUMMARY OF_THE INVENT
The present invention intends to provide a pressure sensitive copy material which can solve the above mentioned problems of the conventional solvent for a coupler and which has an excellent color development performance and a less odor.
;The inventors of the present application have conducted researches on StrDCtUres of alkylene and alkyl groups of various diarylalkanes, thair~physical properties, and relations between these factors and performance in the case 20~ that they are used as the solvents for the coupler in the pressure sensitive copy material. As a result, it has been found that the color development performance is higher when ~the alkylene group is a methylene group than when it is an ethylidene group or an ethylene group, and that the higher the color development performance is, the smaller the number ~ 4 -.
~6~n~
of substituted alkyl groups on a benzene ring is and the lower the branching coefficient of the alkyl group is. In consequence, the present invention has now been completed on the basis of this knowledge.
Moreover, the present inventors have also found that among the C4 alkyl groups, a sec-butyl group is suitable.
That is, the present invention intends to provide a solvent used in the pressure sensitive copy material which is excellent in color development intensity and a color development velocity and which can be manufactured at a low cost.
The present invention is directed to a pressure sensitive copy material using an electron accepting developer and an electron donating coupler which develops a color by contacting with the developer, the pressure sensitive copy material being characterized by employing phenyl-sec-buty~lphenyl-methane~as~a solvent for the electron donating coupler which develops the color by contacting with the electron accepting~developer.
:~20 ~ DESCRIPTIaN OF THE PREFERRED EMBODIMENT
PhenyI-sec-butylphenyl-methane can be prepared by any known method. For example, there are a method of alkylating diphenylmethane by the use of normaI butene in the presence of an acid catalyst, a method of benzylating sec-butylben-zene likewise with the aid of an acid catalyst, a method of condénsing benzene and sec-butylbenzene with formalin, and the like. However, the present invention should not be limited to these methods.
The above mentioned phenyl-sec-butylphenyl-methane can be manufactured more lnexpensively than, for example, phenyl-n-butylphenyl-methane or the like.
Phenyl-sec-butylphenyl-methane has three position isomers of ortho-, meta- and para-compounds owing to substitution positions of the sec-butyl group, and all of these isomers can be used in the present invention.
Nevertheless, the solvent containing plenty of the meta-isomer, the para-isomer or a mixture thereof is desirable from the viewpoints of a color development performance and the like, and the total amount of the meta- and para-isomers in the solvent is preferably 50% by weight or more, more preferably 60% by weight or more. Such a suitable solvent can be easily prepared by altering reaction conditions in the above mentioned manufacturing methods.
The solvent of the present invention can be used, of course, alone and in 50 far as the properties of the solvent itself are not impaired, together with an auxiliary solvent such as a kerosine fraction, an isoparaffinic solvent~ a normal paraffinic solvent, a naphthenic solvent or an alkylbenzene.
In addition thereto, a solvent prepared by mixing the ~3~
phenyl-sec-butylphenyl-methane with another known solvent for a coupler can also be employed in the present invention.
As colorless or nearly colorless electron donating couplers which can develop a color by contacting with a developer, there are typically triarylmethane type com-pounds, diphenylmethane type compounds, xanthene type compounds, thiazine type compounds, and spiropyran type compounds.
The dye-precursors of triarylmethane type compounds are exemplified by 3,3-bis(p-dimethylaminophenyl)-6-dimethyl-aminophthalide (Crystal Violet Lactone), 3,3-bis(p-dimethyl-aminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methyIindole-3-yl)phthallde, 3-~p-dimethylaminophenyl)-3-;~ 15 (2-phenylindole-3-yllphthalide, 3~,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis(1 r 2-dimethylindole-3-yl)~-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl~-S-dimethylaminophthal1de, 3,3-bis(2-phenylindole-3-yl)-5-dlmethylaminophthalide, and 3-p-dimethylaminophenyl-3 (1-methylphrrole-2-yl)-6-dimethy~aminophthalide.
The dye-precursors of diphenylmethane type compounds are exemplified by 4j4-bis-dimethylaminobenzhydrine benzyl ether, N-halophenyl leuco Auramine, and N-2,4,5-trichloro-phenyl leuco Auramine.
The xanthene type dye-precursors are exempllfied by ~, ~
Rhodamine B-anilinolactam, Rhodamine B-(p-nitroanilino)-lactam, Rhodamine B-(p-chloroanilino)lactam, 3-dimethyl-amino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chloro-6-methylfluoran, 3-diethylamino-7-(acetylmethylamino)fluoran, 3-diethylamino-7-(dibenzylamino)-fluoran, 3-diethylamino-7-(methylbenzylamino)fluoran, 3-diethylamino-7-(chloroethylmethylamino)fluoran, 3-diethyl-amino-7-(diethylamino)fluoran, and 3-diethylamino-6-methyl-7-anilinofluoran.
The thiazine type dye-precursors are exemplified by benzoyl leuco methylene blue and p-nitorbenzoyl leuco methylene blue.
The spiro type dye-pxecursors are exemplified by 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphtho-pyran, 3-methylnaphtho-(3-methoxybenzo)spiropyran, and 3-propyl-spiro-dibenzodipyran.
The coupler can be dissolved into the solvent of the i invention in the manner ]ikewise the use of conventional solvents.
As electron accepting color developers, there are clay, polymers, and aromatic carboxylic acids or their metal salts.
The polymers ale exemplified by phenol-aldehyde polymer, phenol-acetylene polymer, maleic acid-rosin .
-polym`er, partially or completely hydrolyzed styrene-maleic anhydride copolymer, partially or completely hydrolyzed ethylene-maleic anhydride copolymer, carboxy polyethylene, and partially or completely hydrolyzed vinyl rnethyl ether-maleic anhydride copolymer.
The examples of aromatic carboxylic acids and their derivatives are exemplified by 3,5-di(~-methylbenzyl)-salicylic acid, 3-(~-methylbenzyl)-5-(~,~-dimethylbenzyl)-salicylic acid, 3-(4'~ dimethylbenzyl)phenyl-5-(~
dimethylbenzyl)salicylic acid, 3,5-di-tert-butyl salicylic acid, 3,5-di-tert-octyl salicylic acid, 3-cyclohexyl-5-(~
dimethylbenzyl~salicylic acid, 3-phenyl-5-(~,~-dimethyl-benzyl)salicylic acid, and 3,5-dit~,Q-dimethylbenzyl)-salicylic acid. Furthermore, their salts of polyvalent metals such as zinc, aluminum, barium, tin, iron, calcium and lead can also be used.
In addition, as the electron accepting developers, there are exemplified by bentonite, zinc oxide, tatanium : oxide, kaolin,~active china clay, acidic china clay, zeolite, talc and colloidal silica.
The above mentioned coupler, when used, is dissolved in a solvent of the present invention, but an amount of the dissoled coupler is generally within the range of 0.5 to 15%
by weight or so.
As the copy material of the present invention, a ~
_ g 63~
pressure sensitive copy material, for example, a pressure senstive copy paper is now picked up, and its generic manufac-turing method will be described: A solution in which the aforesaid coupler is dissolved in the solvent of the present invention is emulsified and dispersed in a mixed aqueous solution of gelatin and gum arabi, and gelatin coatings are then formed around emulsified oil drops by means of the coacervation method. In recent years, an interfacial polymerization, an in-situ polymerization and the like can often be employed for the formation of resin coatings. A first paper is then coated with the thus formed capsule emulsion of the fine oil drops. Afterward, a second paper is coated, on its surfacé which will confront the above coated surface of the first paper, with the aforesaid , 15~ developer, or alternatively the above mentioned first paper is further coated, on the already coupler-coated surface thereof, with the aforesaid developer ln the form of a layer, so that the desired pressure sensitive copy paper can be manu~actured.
Example By the use of a cation exchange resin (Amberlist-15;
Rhoom & Haas Co., Ltd.), diphenylmethane was allowed to react with normal butene in order to prepare phenyl-sec-butylphenyl-methane.
This product had a boiling point of 301 to 312C and a .
~3~2~
kinematic viscosity of 3.9 c.s. at 40C. The total content of meta- and para-isomers in the product was about 80% by weight. In this solvent, CVL which was a coupler was dissolved as much as an amount of 5% to obtain a coupler solution.
This solution was then changed into microcapsules in accordance with the complex coacervation method using gelatin. With the thus obtained microcapsule emulsion, a fine paper was coated to prepare an upper paper.
On the other hand, another paper was coated with a phenolic resin which was a developer, in order to prepare a lower paper.
The prepared upper and lower papers were superposed on each other so that the microcapsule coated surface of the upper paper might face the developer coated surface of the lower paper, and a high pressure press was then driven to develop a color all over the surface.
The lower paper was measured for its reflectance at room temperature by the use of a reflection type spectro-photometer 30 seconds, 60 seconds and 60 minutes after the press operation, in order to thereby obtain color develop-ment intensities.
~ The results are set forth in Table 1. Additionally, the judgment results of odors are listed together.
Each odor judgment result was represented by the total :. -~302~
point of 10 judges on the basis of the standard of "a strong bad odor" being -1 point, "a bad but allowable odor" being 0 point and "no bad odor" being 1 point.
Eor comparison, as diarylethanes having the same carbon S number as in the above Example regarding the present invention, there were used 1-phenyl-1-(isopropylphenyl)-ethane (solvent A), 1-phenyl-2-(isopropylphenyl)ethane (solvent B) and phenyl-tert-butylphenyl-methane (solvent C), and the results are set forth in columns of Comparative Examples 1 to 3 in Table 1. It is apparent ~rom the results therein that the Comparative Examples all had poorer color development properties than in the Example regarding the present invention.
Further, Comparative Examples 4 to 7 were concerned with bicyclic aromatic hydrocarbon solvents having a less carbon atom number than in the ~xample of the present case.
A solvent D was phenyl-xylylethane, a solvent E was phenyl(ethylphenyl)ethane, a solvent F was benzyl-ethyl-benzene and a solvent G was diisopropylnaphthalene.
The solvents E and F were excellent in the color development properties, but were poor in odor inhibition.
The solvent D had poorer color development properties than in the above Example. The solvent G was excellent in odor inhibition but poor in color development properties. In short, the solvents used in the present invention have more . .
~3(1~2~
excellent color development properties and odor inhibition, as compa.red with the conventionally used solvents i.n the Comparative Examples. Comparing with the solvents of Comparative Examples 1, 2, 3, 4 and 7, the excellent color development properties which the solvents of the present invention have are more remarkable at temperatures lower than room temperature.
Table 1 Color Devel.
Intensity (%) Color Devel.
After Aftex After Velocity Solvent 30 sec 60 sec 60 min Ratio(~) Odor _ _ .
Example Better Better Better Better 8 Comparative Example 1 A Good Good Better Good 6
2 B Good Better Better Good 8
3 C Good Better Better Good 7
4 D Good Better :Better Good 6 E Better Better Better Better 5 : 6 F Better Better Better Better 3 7 G Middle Good Better Middle 8 Standard of judgment:
In the heading "Color Development Intensity" in Table ~ ~ 25 1, the respective indications~have the following meanings:
: "Better" = the intensity being 66% or more "Good" = the intenslty being from 61 to 65%
~ ~6~
"Middle" = the intensity being 60% or less Each color development lntensity was obtained as follows: The lower paper was measured for a reflectance before and after the color development, and the color -development intensity was then calculated from the measured reflectance in accordance wlth the following formula:
Color development intensity (%) = (I - Io)/Io x 100 wherein Io and I represent reflectances of the lower paper before and after the color development, respectively.
Therefore, the greater the value from the above formula is, the more excellent the color development intensity is.
In the heading "Color Development Velocity Ratio" in Table 1, the respective indications have the following , meanings:
"Bette~" = the velocity ratio being 96% or more "Good" = the veIocity ratio being from 91 to 95 "Middle" = the velocity ratio being 90~ or less :
~: The color development velocity ratio was a ratio (%) of the color development intensity aftér~ 30 seconds to the intensity after 60 minutes in the heading "Color Development ~; ~ :Intenslty" ln Table 1. Therefore, it is meant that the greater this ratio (%) is, the higher the color development velocity is.
The pressure sensitive copy material of the present , , 3~
invention in which phenyl-sec-butyl-phenyl-methane is used as the solvent for the coupler is characteristically more excellent in color development properties and the odor inhibition in good balance, as compared with the cases where -conventionally known other solvents are used such as phenyl-xylyl-ethane, phenyl-isopropylphenylethane, diiso-propylnaphthalene and phenyl-xylyl-methane. Further, it is also beneficial that the solvent of the present invention can be prepared at a low cost by a usual alkylation.
Furthermore, comparing with the case where the compound having a C4 alkyl group, for example, phenyl-tert-butyl-phenyl-methane is employed as the solvent, the product regarding the present lnvention is more excellent.
: .
.
~: : :
: :
~ ' ...
In the heading "Color Development Intensity" in Table ~ ~ 25 1, the respective indications~have the following meanings:
: "Better" = the intensity being 66% or more "Good" = the intenslty being from 61 to 65%
~ ~6~
"Middle" = the intensity being 60% or less Each color development lntensity was obtained as follows: The lower paper was measured for a reflectance before and after the color development, and the color -development intensity was then calculated from the measured reflectance in accordance wlth the following formula:
Color development intensity (%) = (I - Io)/Io x 100 wherein Io and I represent reflectances of the lower paper before and after the color development, respectively.
Therefore, the greater the value from the above formula is, the more excellent the color development intensity is.
In the heading "Color Development Velocity Ratio" in Table 1, the respective indications have the following , meanings:
"Bette~" = the velocity ratio being 96% or more "Good" = the veIocity ratio being from 91 to 95 "Middle" = the velocity ratio being 90~ or less :
~: The color development velocity ratio was a ratio (%) of the color development intensity aftér~ 30 seconds to the intensity after 60 minutes in the heading "Color Development ~; ~ :Intenslty" ln Table 1. Therefore, it is meant that the greater this ratio (%) is, the higher the color development velocity is.
The pressure sensitive copy material of the present , , 3~
invention in which phenyl-sec-butyl-phenyl-methane is used as the solvent for the coupler is characteristically more excellent in color development properties and the odor inhibition in good balance, as compared with the cases where -conventionally known other solvents are used such as phenyl-xylyl-ethane, phenyl-isopropylphenylethane, diiso-propylnaphthalene and phenyl-xylyl-methane. Further, it is also beneficial that the solvent of the present invention can be prepared at a low cost by a usual alkylation.
Furthermore, comparing with the case where the compound having a C4 alkyl group, for example, phenyl-tert-butyl-phenyl-methane is employed as the solvent, the product regarding the present lnvention is more excellent.
: .
.
~: : :
: :
~ ' ...
Claims (2)
1. A pressure sensitive copy material using an electron accepting developer and an electron donating coupler which develops a color by contacting with said developer, said pressure sensitive copy material being characterized by employing phenyl-sec-butylphenyl-methane as a solvent for said electron donating coupler.
2. A pressure sensitive copy material wherein said pressure sensitive copy material is a copy paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29715685 | 1985-12-26 | ||
| JP60-297156 | 1985-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1263021A true CA1263021A (en) | 1989-11-21 |
Family
ID=17842917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000526101A Expired CA1263021A (en) | 1985-12-26 | 1986-12-22 | Pressure sensitive copy material |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4879269A (en) |
| EP (1) | EP0229372B1 (en) |
| JP (1) | JPH07102736B2 (en) |
| CA (1) | CA1263021A (en) |
| DE (1) | DE3670987D1 (en) |
| ES (1) | ES2015528B3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990001417A1 (en) * | 1988-08-09 | 1990-02-22 | Nippon Petrochemicals Co., Ltd. | Pressure-sensitive copying material |
| JP2946233B2 (en) * | 1990-07-10 | 1999-09-06 | 日本石油化学株式会社 | Pressure-sensitive copying material |
| US5084433A (en) * | 1990-11-21 | 1992-01-28 | Minnesota Mining And Manufacturing Company | Carbonless paper printable in electrophotographic copiers |
| US5318940A (en) * | 1992-12-02 | 1994-06-07 | Koch Industries, Inc. | Carbonless paper solvent comprising diisopropylbiphenyl and triisopropylbiphenyl and products utilizing same |
| US5866514A (en) * | 1995-07-11 | 1999-02-02 | Nippon Petrochemicals Company, Limited | Pesticidal composition to noxious organisms |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US32162A (en) * | 1861-04-23 | George s | ||
| JPS492126B1 (en) * | 1970-10-27 | 1974-01-18 | ||
| CA986714A (en) * | 1971-03-02 | 1976-04-06 | Yoshiaki Aida | Pressure-sensitive record material employing diaryl alkane solvents |
| IT966722B (en) | 1971-03-02 | 1974-02-20 | Nippon Petrochemicals Co Ltd | SOLVENT FOR REPRODUCTION MATERIAL GRAPHICS SENSITIVE TO PRESSURE TRACING PAPER AND METHOD FOR ITS PREPARATION |
| JPS5636074B2 (en) * | 1972-03-07 | 1981-08-21 | ||
| US3996405A (en) * | 1973-01-24 | 1976-12-07 | Ncr Corporation | Pressure-sensitive record material |
| JPS5711085A (en) * | 1980-06-25 | 1982-01-20 | Nippon Petrochem Co Ltd | Recording material |
-
1986
- 1986-12-22 DE DE8686117894T patent/DE3670987D1/en not_active Expired - Lifetime
- 1986-12-22 CA CA000526101A patent/CA1263021A/en not_active Expired
- 1986-12-22 ES ES86117894T patent/ES2015528B3/en not_active Expired - Lifetime
- 1986-12-22 EP EP86117894A patent/EP0229372B1/en not_active Expired
- 1986-12-26 JP JP61313175A patent/JPH07102736B2/en not_active Expired - Lifetime
-
1989
- 1989-04-03 US US07/333,791 patent/US4879269A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07102736B2 (en) | 1995-11-08 |
| US4879269A (en) | 1989-11-07 |
| JPS62234983A (en) | 1987-10-15 |
| EP0229372B1 (en) | 1990-05-09 |
| ES2015528B3 (en) | 1990-09-01 |
| EP0229372A1 (en) | 1987-07-22 |
| DE3670987D1 (en) | 1990-06-13 |
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